Polymers derived from diamines or aminoalcohols and trialkyl or triaryl phosphites



United States Patent 3,377,409 POLYMERS DERIVED FROM DIAMINES 0R AMI- NOALCOHOLS AND TRIALKYL 0R TRIARYL PHOSPHITES Richard L. McConnell and Harry W. Coover, Jr., Kingsport, Tenm, assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Continuation of application Ser. 0. 271,884, Apr. 14), 15363. This application Oct. 17, 1966, Ser. No. 587,945

8 Claims. (Cl. 260--926) ABSTRACT OF THE DISCLOSURE Flame-resistant linear and cross-linked phosphoruscontaining polymers are prepared from the reaction of [A] an organic phosphitee.g., triethyl phosphite, triphenyl phosphite, and [B] a compound having at least one amino group-e.g., ethylenediamine, 1,4-cyclohexanebis(rnethylamine), S-aminopentanol.

This application is a continuation of Ser. No. 271,884 filed Apr. 10, 1963, now abandoned.

This invention relates to new polymeric materials containing phosphorus, and to their preparation. The invention particularly concerns both linear and cross-linked polymers derived from the reactions of certain organic phosphites with certain compounds containing at least one anino group.

The linear polymers of the invention contain the recurring group represented by the formula:

RPR

wherein R is selected from the group consisting of a monovalent aliphatic radical, a monovalent alicyclic radical and a monovalent aryl radical,- and wherein R is a divalent radical selected from the group consisting of:

i i i NRN' -NRO-- wherein R is selected from the group consisting of a divalent alicyclic radical, a divalent aryl radical, a divalent aliphatic radical and hh hh 3,377,499 Patented Apr. 9, 1968 2 The cross-linked polymers of the invention contain the recurring group represented by the formula wherein R is as defined above and Y is a divalent substance selected from the group represented by the formulas Heretofore, it was thought that heating a mixture of a phosphite, for example, a trialkyl phosphite and a diamine or aminoalcohol would result in alkylation of the amine rather than formation of a linear polymer. Consequently, the polymers of the present invention which are of high molecular weight and highly flame resistant were not considered possible.

A principal object of the invention, therefore, is to provide new phosphorus-containing polymers useful in their linear states and capable of cross-linking to dimensionally stable, insoluble products forrnable into fibers, sheets and films. Further objects shall become apparent from the following description and claimsi p The linear polymers having the above general formula are obtained according to the following reactions:

Also according to the invention, the phosphorus-containing reaction products obtained by using a mixture of and containing both amino and alcohol end groups may be reacted with diisocyanates to give products having recurring structural units such as E below:

wherein R, R, R" and Z are as defined above.

In preparing the cross-linked polymers having recurring groups of the formula:

Suitable phosphites which may be used in this inven-.

tion include the trimethyl, triethyl, tributyl, triisobutyl, trioctyl, tris(2-ethylhexyl), trilauryl, triphenyl, tritolyl, and tricyclohexyl phosphites. It is also possible to use mixed phosphites such as the methyldiethyl, ethyldibutyl, ethyldiphenyl, 2-ethylhexyldiphenyl, and diphenyltolyl phosphites.

Suitable diamines which may be used as in this invention include aliphatic ethylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,10-decanediamine, and 1,12-dodecanedia1mine.

Also, alicyclic diamines such as in which Z is H, alkyl, cycloalkyl, or aryl, and R is a divalent hydrocarbon group. Examples of such aminoalcohols include 2-aminoethanol,

3-aminopropanol,

4-a-minobutanol,

4-aminopentanol,

S-aminopentanol, 3-arnino-2,2-dimethyl-l-propanol, 6- arninohexanol,

S-aminooctanol, 4-amino-1-cyclohexanol, 4-aminomethylcyclohexanemethanol, N-ethylaminoethanol, S-(ethylamino)-2,2-dimethyl-l-propanol, p-aminophenol,

N-phenylaminoethanol, and 3-amino-2,2,4,4-tetramethyl cyclobutanol.

In order to obtain high-molecular-weight products, it is desirable to use approximately equimolar amounts of the phosphite and the diamine or the :aminoalcohol; however, it is sometimes desirable to use an excess of the diamine or aminoalcohol so that a product containing amino or hydroxy end groups may be obtained. Such products, as mentioned above, may be subsequently reacted with diisocyanates to produce high-melting polyureas or polyurethanes. It is sometimes desirable to use a mixture of two or more diamines to impart certain specific properties to the phosphorus-containing polymers.

In general, the condensation of the diamine with the phosphite is conducted in the absence of a solvent. Inert solvents may be used, however, if desired. The operable temperature range of this reaction is about -25 C. to about 300 C. In general, the condensations are initiated at room temperature and completed at a somewhat higher temperature, for example, final temperatures of approximately 250 C. are especially suitable. Catalysts are not required for the reaction. It is advantageous to use decreased pressure toward the end of the reaction in order to remove the liberated alcohol or phenol. The end products are either extremely viscous liquids or white solid products.

If a product containing amino or both amino and alcohol end groups is reacted with a diisocyanate, it is advantageous to use an inert solvent such as the hydrocarbons, ethers, esters, and ketones, since the reactions are extremely exothermic. In this final condensation, it is advantageous to have equivalent amounts of the diisocyanate and the intermediate organophosphorous material in order to obtain high-molecular-weight polymers.

The following examples will further serve to illustrate the invention.

Example 1.Polymer derived from triethyl phosphite and 1,6-hexanediamine Anhydrous 1,6-hexanediamine (0.2 mole) was mixed with triethyl phosphite (0.2 mole) and heated in the presence of nitrogen. As the reaction temperature reached approximately C., ethyl alcohol was liberated. The evolved ethyl alcohol was distilled from the reaction mixture as formed. The reaction was conducted until the theoretical amount of ethyl alcohol had been liberated (0.4 mole). The maximum reaction temperature used was 250 C. and vacuum was employed during the later stages of the reaction to remove the last traces of ethyl alcohol. This polymeric material was an extremely viscous, colorless oil at 250 C. and a white solid at 25 C. An infrared spectrum of the product indicates bands for -NH groups and POC H groups, and this spectrum is compatible with the recurring structure I"NHCHzCHzCHaCIIzCHaCHzNH \0 Calls )1:

Similar polymeric materials are obtained when triethyl phosphite was treated with l,4-cyclohexanebis (methylamine), p-phenylenediamine, and N,N'-dimethyl-1,6-hexanediamine. Similar results were also obtained when trimethyl phosphite, trilauryl phosphite, triphenyl phosphite, and ethyl diphenyl phosphite were used instead of triethyl phosphite.

Example 2.Polyurea from the reaction product of triethyl phosphite and 1,6-hexanediamine Similar polymers were obtained using 4,4-diphenylmethane diisocyanate and 1,4-cyclohexylenedimethylene isocyanate instead of the 2,4-tolylene diisocyanate.

Example 3.-Polymer derived from triethyl phosphite and 4-aminomethylcyclohexanemethanol Triethyl phosphite (0.2 mole) and 4-aminomethylcyclohexanemethanol (0.2 mole) were reacted according to the procedure described in Example 1 to produce a polymeric product which may be represented by the recurring structural unit Similar results were obtained using other trialkyl or triaryl phosphites and other aminoalcohols.

Example 4.-Polyurethane from the reaction product of triethyl phosphite and 5-aminopentanol Triethyl phosphite (0.2 mole) and S-aminopentanol (0.23 mole) were reacted according to the procedure of Example 1 to produce a low-molecular-weight prepolymer. When this material was treated with hexamethylene diisocyanate, a high-molecular-weight polymer was formed which consisted essentially of the recurring structural unit Similar results were obtained using 4,4 diphenylmethane diisocyanate, 2,4 tolylene diisocyanate, or 1,4- cyclohexylenedimethylene isocyanate instead of the hexamethylene diisocyanate.

Example 5.--Polymers derived from triphenyl phosphite and 1,4-cyclol1exeanebis (methylamine) Triphenyl phosphite (0.1 mole) and 1,4-cyclo'hexanebis(methylamine) (0.1 mole) were mixed and heated to 180 C. with stirring for 1.5 hours in the presence of dry nitrogen. The temperature of the reaction mixture was lowered to 120 C. and vacuum was gradually applied to remove the liberated phenol. The temperature was gradually raised to about 180 C. at a pressure of about 1 mm. of Hg. and maintained under these conditions until the theoretical amount of phenol (0.2 mole) had been removed. The viscosity of the melt increased as the reaction proceeded and the final melt is an extrernly viscous,

light amber oil at 200 C. The molecular weight of this product is greater than 1000 and its structure may be repsented by the recurring structural unit Similar results were obtained using butyl diphenyl phosphite or dibutyl phenyl phosphite instead of the triphenyl phosphite except that a mixture of butyl alcohol and phenol was removed during the course of the reaction rather than phenol alone. The reaction was repeated except that 0.1 g. of sodium methoxide was added to the reaction mixture. The sodium methoxide acted as a cata lyst and accelerated the removal of the phenol. Other compounds found to have a catalytic effect included sodium phenoxide, sodium amide, lithium phenoxide, zinc acetate and diphenyl hydrogen phosphite.

Example 6Cross-linked polymer derived from triphenyl phosphite and N,N dimethyl 1,4-cyclohexane-bis (methylamine) Triphenyl phosphite (0.2 mole) and N,N'-dirnethyl-1,4- cyclohexanebis(methylamine) (0.3 mole) were reacted according to the procedure of Example 5 except that the maximum reaction temperature was 200 C. A total of 0.51 mole of phenol was removed during the reaction and this cross-linked product may be represented by the recurring structural unit NCHa Treatment of this polymer with hexamethylene diisocyanate yielded a highly cross-linked material which is insoluble and infusible The reaction was repeated using 0.1 g. of sodium methoxide as a catalyst to facflitate the removal of the phenol. Similar results were obtained using sodium diphenyl phosphite and also diphenyl hydrogen phosphite as catalysts. Similar results were also ob tained when piperazine was used instead of the N,N'- dimethyl 1,4 cyclohexanebis(methylamine).

Example 7.-Po1ymer derived from tricyclohexyl phosphite and 2,2,4,4-tetramethylcyclobutanediamine Tricyclohexyl phosphite (0.2 mole) and 2,2,4,4-tetramethylcyclo'outanediamine (0.2 mole) were reacted according to the procecdure of Example 5 to liberate cyclohexanol and produce a polymeric material which may be represented by the recurring structural unit CH3 OH;

CsHn C 3 CH3 Similar results were obtained using dicyclohexyl ethyl phosphite, cyclohexyl diphenyl phosphite or butyl cyclohexyl tolyl phosphite instead of the tricyclohexyl phosphite.

Example 8.-Cross-linked polymer derived from tritolyl phosphite and 3 (methylamino)-2,2-dimethyl-1-propanol Tritolyl phosphite 0.2 mole) and 3-(ethylamino)- 2,2 dimethyl 1 propanol (0.3 mole) were reacted according to the procedure of Example 5. A total of 0.52 mole of cresol was removed during the reaction and the cross-linked light amber product may be represented by the recurring structural unit Treatment of this polymer with tolylene diisocyanate gave a highly cross-linked material which is insoluble and infusible.

Example 9.Polymer derived from triphenyl phosphite and 4-,4'-methylenebis(3-chloroaniline) Triphenyl phosphite (0.1 mole) and 4,4'-methylenebis(3-chloroaniline) (0.1 mole) were reacted according to the procedure of Example 5. The theoretical amount of phenol (0.2 mole) was removed and the structure of this solid polymeric product may be represented by the recurring structural unit Similar results were obtained when 4,4 methylenebis(3 bromoaniline) or 4,4 methylenebis(2,5-dichloroaniline) were used instead of the 4,4'-methylenebis(3-chloroaniline).

and

Similar results are obtained using other molar ratios of triphenyl phosphite and diphenyl hydrogen phosphite. For example, the molar ratio of triphenyl phosphite to diphenyl hydrogen phosphite may be varied from 95/5 to 5/95. Similarly good results are obtained using mixtures of trialkyl and dialkyl hydrogen phosphites such as mixtures of triethyl phosphite and diethyl hydrogen phosphite, mixtures of tributyl phosphite and dibutyl hydrogen phosphite or mixtures of triphenyl phosphite and dibutyl hydrogen phosphite. Similar results are also obtained using an aminoalcohol such as 4-aminoniethylcyclohexanemethanol instead of the diamine.

The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can vbe effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows: 1. Linear polymers containing the recurring group RPR wherein R is selected from the group consisting of an alkyl radical, a cycloa'lkyl radical, and an aryl radical, and wherein R' is a divalent radical selected from the group represented by the formulas Z t i -I I-RN- and -N-RO wherein R" is selected from the group consisting of an alkyl radical, a cycloalkyl radical, and an aryl radical,

and

wherein x is selected from the group consisting of a hydrogen atom, an alkyl radical, a cycloalkyl radical, and an aryl radical, wherein h is selected from the group consisting of a hydrogen atom, a chlorine atom, and a bromine atom, and wherein Z is selected from the group consisting of a hydrogen atom, an alkyl radical, a cycloalkyl radical, and an aryl radical.

2. The polymeric product of the reaction of triethyl phosphite with Lo-hexanediamine, said product being an extremely viscous, colorless oil at 250 C. and a white solid at 25 C., and containing the recurring unit of the formula 3. The polymeric product of the reaction of triethyl phosphite with 4-aminomethylcyclohexanemethanol, said product containing the recurring unit of the formula 4. The polymeric product of the reaction of triphenyl phosphite with 1,4-cyclohexanebis(methylamine), said product containing the recurring structural unit of the formula.

5. The process comprising reacting, in at least approximately equimolar amounts and at a -temperature within the range of from about 25 C. to about 300 C., a phosphite having the general formula (ROMP wherein R is selected from the group consisting of a saturated monovalent aliphatic radical, a saturated monovalent alicyclic radical, and a monovalent aryl radical of the benzene series with compound having a general formula selected from the group consisting of Z t i HN-R"NH and HNR"-OH wherein R" is selected from the group consisting of a saturated divalent aliphatic radical, a saturated divalent al'icyclic radical, a divalent aryl radical of the benzene series, and

wherein x is selected from the group consisting of a hydrogen atom, a saturated monovalent aliphatic radical, a saturated monovalent alicyclic radical, and a monovalent 11 7. The polymeric product of the reaction of triphenyl phosph'ite and 4,4'-methyleneb is(3-chlo-noaniline), said product containing the recurning unit of the formula 8. Cross-linked polymers containing the recurring group and wherein R is a divalent radical selected from the group represented by the formulas I l NRN and NR-O wherein R" is selected from the group consisting of an alkyl radical, a cycloalkyl radical, and an aryl radical, and

11 h h h wherein x is selected from the group consisting of a hydrogen atom, an alkyl radical, a cycloalkyl radical, and an aryl radical, wherein it is selected from the group consisting of a hydrogen atom, a chlorine atom, and a bromine atom, wherein Z is selected from the group consisting of an alkyl radical, a cycloalkyl radical, and an aryl radical, and wherein Y is a divalent substance selected from the group represented by the formulas i l NRN and --NR-O wherein R" and Z are as defined a bove.

No references cited.

CHARLES B. PARKER, Primary Examiner. R. L. RAYMOND, Assismnt Examiner. 

